Anti-emulsion agents in the separation of olefins



slung mAH- Nov. 6, 1962 .1. T. MACHT Erm. 3,062,907

ANTI-EMULSION AGENTS IN THE SEPARATION OF OLEFINS Filed July 6, 1959 2Sheets-Sheet 1 Nov. 6, 1962 .1.1'. MACHT Erm.A 3,052,907

ANTT-EMuLsToN AGENTS 1N THE SEPARATION oE oLEFINs mi Mv N Q h,

Filed July 6, 1959 United States Patent wie@ man Nizoei 3,062,907ANTI-EMULSION AGENTS IN THE SEPARATON OF OLEFINS .lohn T. Macht, 830Elmhurst St., and Charles M. Fingan, 493 Lake Shore Road, both ofSarnia, Ontario, Canada Filed July 6, 1959, Ser. No. 825,182 8 Claims.(Cl. 260-6815) This invention relates to certain anti-emulsion agentsparticularly suited for' preventing emulsion formation and for breakingemulsions in a specific industrial application. This application is acontinuation-in-part of our copending and now abandoned applicationSerial No. 597,695, tiled July 13, 1956.

It is now well known that butadiene-1,3 is an especially valuablecommercial chemical since it can be polymerized either alone or togetherwith other materials to form a variety of polymeric materials; anexample is the copolymerization of butadiene-1,3 and styrene to form asynthetic rubber known as GR-S. Butadiene-1,3 may be conveniently formedby the dehydrogenation of n-butylene using, for example, a calciumnickel phosphate catalyst, of the type disclosed in United States PatentNo. 2,442,- 320, issued May 25, 1948, to Andrew I. Dietzler et al., inthe presence of steam. The product of the dehydrogenation usuallycontains about 18 to 25 weight percent butadiene-1,3 with the remainderbeing unreacted in nbutylene and other hydrocarbons. In order to obtainsubstantially pure butadiene-1,3 for use as a polymerizable monomer, itis therefore necessary to separate the butadiene-1,3 from thecontaminants.

One satisfactory method of separating olenic hydrocarbons containingatleast four atoms in the olefmic chain from other hydrocarbons, forexample, separating butadiene-1,3 from other hydrocarbons, is acountercurrent solvent extraction such as the one disclosed in U.S.Patent 2,459,451 to Packie et afl. The mixture of hydrocarbons is rstthoroughly mixed in a mixing chamber with a preferential solvent for thehydrocarbon being separated; a suitable solvent is an ammoniacalsolution of copper ions with an anion capable of forming cuprous saltssoluble in the ammoniacal solution. Anions which have been suggested asbeing suitable include sulfate, phosphate, acetate, lactate, tartrate,formate, borate, carbonate, chloride, iluoride, glycolate,thioglycolate, salicylate, benzene sulfonate, orthophosphate, cyanide,thiocyanate, maleate, etc. One example of such solvent which was enjoyedwidespread use is aqueous copper ammonium acetate. The mixture is thenpassed to a settling chamber where the hydrocarbon-enriched solventseparates from the hydrocarbons.

A more complete outline of the process of extracting butadiene-1,3 withaqueous copper ammonium acetate solvent may be represented in thefollowing manner. Conventionally, the process is carried out in a seriesof mixers and settler tanks with each mixer having an associated settlertank. The point of entry of the aqueous copper ammonium acetate solventis usually at one end of this series, while the point of entry of thebutadiene-1,3 containing hydrocarbon stream is conventionally at amixersettler unit located at a point intermediate the point of entry ofthe aqueous copper ammonium acetate solvent and the opposite end of themixer-settler chain. The direction of low of the hydrocarbon stream iscounter-currentto-the direction of Aflow of the aqueous copper amvtheaqueous copper ammonium acetate solvent.

monium acetate solvent. Thus the butadiene-1,3-containing liquidhydrocarbon stream which is being subjected to extraction is thoroughlymixed with the aqueous copper ammonium acetate solvent in a mixer at thepoint of entry of the hydrocarbon into the extraction chain. The mixtureis pumped from the mixer to its adjoining settler tank, Where the twophases are allowed to separate. The upper, or hydrocarbon, phase goes tothe next mixer-settler unit in the direction of the point of entry ofthe aqueous copper ammonium acetate solvent where it is furtherextracted with fresher solvent. The lower, or solvent, phase goes to thenext mixer-settler unit in the direction away from the point of entry ofthe aqueous copper ammonium acetate solvent, where it is used to extractseparated hydrocarbon obtained from a settler further removed down thechain. The temperature becomes higher in each unit in the direction offlow of This serves to raise the purity of the butadiene-1,3 dissolvedin the solvent and to increase the concentration of butadiene-1,3 in thehydrocarbon phase by rejecting more dissolved butadiene-l,3 and otherhydrocarbons from the aqueous copper ammonium acetate phase to thehydrocarbon phase. Since the direction of flow of the hydrocarbon streamis counter-current to that of the aqueous copper ammonium acetatesolvent stream, it is evident that the butadiene-1,3 content of thehydrocarbon phase is lowest in the settler tank nearest to the point ofentry of the solvent into the mixer-settler chain, and highest in thesettler furthest removed.

It has been found, however, that the rate of separation of thehydrocarbon-enriched solvent from the hydrocarbon in the settler tankswas slow, because of the presence of emulsions.

It is therefore an object of the present invention to discloseanti-emulsion agents which are suitable in the breaking of emulsions andin the inhibition of emulsion formation in a system comprising ahydrocarbon phase and a hydrocarbonenriched solvent phase, such solventbeing an aqueous ammoniacal solution of copper ions with an anioncapable of forming copper salts soluble in such ammoniacal solution. l l

It is a more particular object of the present invention to provide ananti-emulsion agent suitable for the breaking of emulsions and for theinhibition of emulsion formation in a system consisting of a phasecomprising C., hydrocarbons which may contain either low or highlconcentrations of butadiene-1,3, and a phase comprising an aqueousammoniacal solution of copper acetate containing dissolvedbutadiene-1,3.

These and other objects of the present invention are achieved in theprocess of separating an olefin having at least four carbon atoms in theoleiinic chain from a mixture of said olelin and other olenic andsaturated hydrocarbons (for example separating butadiene-1,3 from amixture of butadiene-1,3 and other oleinic and saturated hydrocarbonssuch as, n-butylene, butanes and isobutylene), and which includes thesteps of intimately mixing the hydrocarbon mixture with a solventcomprising an ammoniacal solution of copper ions with an anion capableof forming cuprous salts soluble in said ammoniacal solution (forexample an aqueous copper ammonium acetate solvent), and allowing themixture of solvent and hydrocarbon to separate into a hydrocarbon phaseand an olefin-enriched solvent phase in a settler tank (for ex- 'fonatedfatty acid (which contains 5-25 carbon atoms) amide derivative.

Of the anionic surface active agents found to be effective in thepresent invention, the following are preferred in the practice of thisinvention:

('1) Fatty alcohol amine sulfates, c g., the triethanolamine salt oflauryl alcohol sulfate, or tr-iethanolamine lauryl sulfate,

(2) The nitrogen containing salts of alcohol sulfates, e.g., theammonium salt of lauryl alcohol sulfate, ammonium lauryl sulfate, or thetriethanolamine salt of lauryl alcohol sulfate; and

(3) The sulfonated fatty acid amide derivatives, either alone or thesulfonated fatty acid amide mixed with an aryl alkyl sulfate and havingan infra-red spectrum simi- `lar to that shown in the graph of FIG. l.

In this specification, the Iterms anionic, non-ionic and cationic areused in their accepted meanings. Thus, the anionic compounds are thosewhich are ionized in solution with the active portion of the moleculebeing nega- 'tively charged land moving in solution towards the anode.

The anionics consist principally of the sulfated and sulfonatedcompounds which can be subdivided -into the following categories:alkyl-aryl sulfonates; alkyl sulfates;

sulfated and sulfonated amines and amides; sulfated and sulfonatedesters and ethers; alkyl sulfonates; and miscellaneous types.

The cationic compounds are those in which the active part of themolecule Iis positively charged and hence moves in solutions towards thecathode. The cationics generally are weak in detergent power but lmainlyhave strong -lubricating Vand germicidal properties. They fall into twomain classes: acid neutralized tertiary amine salts; and quaternaryammonium compounds.

Those compounds which do not ionize in solution are known as non-ionics.They are generally insoluble in water and are chiefly emuisifyingagents. The two main types are esters and ethers, the ether sometimesbeing present in a group of polyalcohols on ethylene oxide. Thehydrophobic part of the chain may be an acid, alcohol, phenol, amide oramine.

Before illustrating the present invention by reference to examples, testI will be described in which various agents were tested foranti-emulsion activity under conditions similar to actual commercialoperating conditions. The `following procedure was used in carrying outthe test:

A Ispecific amount of the solvent, an example of which is copper'ammonium acetate, is agitated at 8 P. with C4 hydrocarbons for twominutes. The top level of the emulsion is read immediately, and the timein seconds recorded for the top level to drop to the half-volume mark ofthe emulsion. That length of time is known Ias the emulsion time of theC4 hydrocarbon used. In order to determine the effect of theanti-emulsion agent, the required amount of anti-emulsion agent is addedto the solvent prior to the agitation thereof with the same C4 hydro-Ycarbons. The emulsion time is then an indication of the lrenthesesindicates the manufacturer of the trade named product.

The initial solvent emulsion time is 135 seconds.

4 TABLE 1 Evaluation of Surface Active Agents for Breaking Emulsions inCopper Ammonium Acetate-Hydrocarbon Mixtures SURFACE ACTIVE AGENTNon-Ionic Concentration (p.p.m. on solvent) 500 1,000

No. Trade name Chemical Emulsion time composition (Seconds) 1-.--Alrosol B (Alrose Fatty alkylol amide 300 Chemical Co.). condensate.2---. Alrosol C (Alrose -.--.do 200 300 Chemical 0o.). 3...- Antal-ox400 (Antara Alkyl aryl polyoxy 300 Chemicals DW. ethylene glycol.General Dyestui Corp). 4--.- Atlosene 50G-C (Atlas Fatty alkylol amide300 Refinery Inc.) condensate. 5...- Atlox 1096 (Atlas Polyoxyethylene387 300 Powder 0o.). fatty esters. 6.... D-Sperso-W (Plane- Polyglycol,fatty 266 300 tary Chemical 0o.). acid, sodium sullosuccinic acidcondensate. 7--.- Nil Dodecyl alcohol 150 120 120 8.... Emulphor VN-430Polyoxyethylated 160 300 Genci-al Dyestutl fatty acid.

orp. 9-... Emulphor EL-719 Polyoxyethylated 165 300 Genefsd Dyestutvegetable oil.

orp. 10.-. Emulsifier S10-A Polyoxyethylene 300 (Victor Chemical glycolfatty acid Works) ester. 11... Energetic (Armour Polyoxyethylenc 300 ano. ester of fatty acids, 12... Hydroterg B (Hydro- Fatty alkanol 200carh)on chemicals amide.

c. 13... Igepal Cit-030 Iso-octyl phenoxy 300 (General Dyestuipolyoxycthylene Corp.). alcohol. 14... Kessco 23201 Polyglyeol ether13() 175 230 (Kessler Chemical ester of fatty 0o.). acids. 15...Nome-218 (Sharples Polyethylene glycol 300 Chemicals Inc.). tetdodeeylthioet er. 1G... Nonisol 100 (Alrose Polyethylene glycol 230 300Chemical 0o.). of lauric acid. 17-.. Permoleue A-122 Fatty amide con-240 220 (Refined Products densate, fatty Coro). esters and salts offatty alcohol sulfates. 18.-- Pluronic L-62 Ethylene oxide, 300

(Wyandotte Chempropylcne oxide, ical. Corp.). condensate. 19... SponieAP (Amer- Allrylphenol ether... 300

iean Alcolac Corp.). 20... Sterox-CD (Mon- Polyoxyethylene 180 100sCant)o Chemical ester.

o. 2l... Sterox SK (Mon- Polyoxyethylene 150 300 sant thioether. 22...Surfynol 82 (Air Ditertiary acety- 170 130 120 Reduction Chemlenicglyeols. ical 00.). 23.-. Surfyno1102 (Air .do 120 125 ReductionChemical 00.). 24.-. Surfynol 104 (Air .-..,do 160 165 169 ReductionChemical Co. 25... Synthetics .AD- Polyethylene glycol 300 (HerculesPowder ether of hydro- Co.). abietyl alcohol. 26--. Tween 20 (Atlas Pow-Polyoxyethylene 300 der Co. sorbitan monolaurate. 27... Tween 81 (AtlasPow- Polyoxyethylene 30o der Co. sorbitan monooleate.

Cationic 28-.- Alkaterge-C (Comsubstituted oxazo- 200 300 mercialSolvents line. Corp.).

20.-. Katapol VP-532 (At- Alkyl polyoxyethy1- 140 300 las Powder 0o.).eue glycol amine. `30... Miranol-OH (Mira- Lam-oyl imidazo- 300 nolChemical 0o.). ltelfie hydroxy acea e. 31.-. Negamine-MZA Amine ester oflong 240 300 (Synthetic Chemchain fatty acid.

icals lue). 32... Quatronyx (Onxy Oil Alkyl dimethyl car- 215 300 andChemical 0o.). boxy methyl ammonium chloride.

SURFACE ACTIVE AGENT- Continued Anionics-Alkyl, Aryl, Sulfonates andSulates' Concentration (p.p.m. on solvent) 100 500 1,000

No. Trade name Chemical Emulsion time composition (seconds 33.-- AhcoWetANS (Arn- Alkyl aryl sodium 220 180 ild )Henman and sulfonate.

o. 34... Alkanol WXN (E. l. Sodium alkylaryl 215 285 uont de N amourssulfonate.

o. 35... Alrosperse 40K (Alrose Alkyl naphthalene 285 Chemical 0o.).sodium sulfonate. 3G... Aresklenc 375 (Mon- Dibutyl phenyl 300 santoChemical phenol sodium $30.). disulfonate. 37--. Dlanol ll (Quaker Alkylaryl sulfonate. 265 300 Chemical Products Corp. 38... Dexolene B (DexterSodium dioctyl 205 200 Chemical Corp.)l sulfosuccinate. 39... Dexolene G(Dexter do 195 175 Chemical Corp). 40... Dexolene MTN .do 300 (DexterChemical Corn). 4l.-. Merpentine (El. du Alkyl naphthalene 170 200 Pontde Nemours sulfonate.

& 0o.). 42.-. Morcovi'et 469 (Mordo 220 300 ton Withers Chemical Co.).43. Moropon-DB Amine alkyl aryl 225 190 (Moretex Chemisulfate. calProducts). 44.-. Naxouate 4L (Wyan- Sodium xylene 135 130 dotte Chemicalsulfona-te. Coro). 45... Nekal NF (Monsanto Alkyl naphthalene 155 300Chemical Corp.). sulionate. 46... Neomerpin (El. du do 160 190 Pont deNemours & 0o.), 47... Neornerpin N (El. Alkylated naphtlia- 160 215 duPont de Nelene sulfonic acid. mours & 0o.). 48.-. Niuex 300 (Ninol Alkylaryl sodium 180 150 Laboratories 1110.). sulfonate. 49.-. Santomcrse 30X.do 180 l5() (Monsanto Chemical 0o.). 50... Sulfanole KA (War- Alkylaryl sulfonate. 255 260 wick Chemical Co. Div. San Chemical Corp.).51... Sulframin KE (Ultra .do 170 255 Chemical Works). 52-.. Titazole SA(Titan Sodium aryl naph- 160 165 ghenical Products, tlialene sulfonate.

c. 53-.. Triton X-200 (Rohm Sodium salt of alkyl 280 300 and Haas 0o.).aryl polyester sulfonate. 54.-. Triton W-30 Conc. Alkyl aryl poly- (Rohmand Haas ether sulfate iso- Co.) propanol.

Sulfated or Sulfonated Alcohols, Arnides Amines, and Esters 55.-.Ahcowet RS (Arnold, Sulfated fatty acid 19D 300 Holman and 0o.). ester.56... Alipal CO-436 (Gen- Ammonium salt of 160 20 eral Dyestui sulfateester of an Corp). alkyl phenoxy polyoxyethylene ethanol. 57--. AlkamineD (Amal- Sulfatcd fatty 200 160 105 gamated Chemical alcohol. Corp.).58... Avitex AD (El. du Sulfated alcohol 135 165 205 Pont de Nemoursderivative. & Co.). 59--. Carbase Emulsier Sulfonated petro- 210 245Ca1)lisle Chemical leum base.

nc. 60-.. Compound 8-5 (J ohn- Sodium salt of an 145 300 son-MarchCorp.). alkfl sulfonic aci 61.-. Dergon T (Arkansas Fatty acid ester 250140 Co. sulfate. 62..- Dianol 20 (Quaker Ester sulfate 190 300IClhomical Products c. 63.-- Duponol GS (EJ. du Fatty alcohol amine 13479 52 Pont de Nemours sulfate. i 0o.). 64... Dynesol F-20 (Amal-Sulfonated poly- 240 255 gamated Chemical ester of an Corp.) aliphaticalcohol. 65-.. EmKapon K Amide sulfonate,- 255 255 Emkay Chemical o.66..-. Estersulf X (Maher Alkane sulfonamide- 255 255 golor & ChemicalSURFACE ACTIVE AGENT-Continued Concentration (p.p.1n. on solvent) 5001,000

N o. Trade name Chemical Emulsion time composition (Seconds) 67.-.Mirapon RK Conc. Sulfonated fatty 66 55 (Miranol Chemical acid amidemixed Co.) with an alkyl aryl sulfonate. 68... Miranol LF Liquid Apolyamine deriv- 196 300 Conc. (Miranol ative of a sulfo- Chemical Co.).nated fatty acid amide. 69.-. Nopco 2031 (Nopco Sulfated hydroxy 300Chemical Co.). stearic acid. 70.-. Orvus K (Proctor & Modified alkyl 210270 Gamble Distrisulfate. buting,r 0o.). 71... Petrowet R (El. duSaturated hydro- 170 116 92 logt de Nemours carbon sulfonate. L O. 72.-.SD-70 (Laurel Soap Ester sulfate 300 300 Mfg. 00.). 73.-. Sipon LT-oTriethanolamine 95 48 36 (American Alcolac salt of lauryl Corp). alcoholsulfate. 74.-. Sipon L-22 (Ameri- Ammonium salt oi 158 69 41 can AlcolacCorp.). lauryl alcohol sulfate. 75.-. Stepanol B-153 Ammonium alkyl 165195 (Stepan Chemical phenoxy polyoxy- 0o.). ethylene sulfate. 76..`Suliramin DR (Ultra Sodium salt of an 156 158- 138 Chemical Works).hydroxy alkyl amido alcohol sulfate. 77... Synthogel (Synthron Sodiumsalt of a 159 153 166 Inc). substituted l amido-ethyl sulfonatc. 78.-.Tergcnol G (Hart A modified alkyl 240 Products Corp.). sulfate.

79..- Tergitol 08 (Carbon Sodium sulfate 160 and Carbide derivative ofChemicals 0o.). ethyl hexanol. 80... Trepenol T-100 Trietlianolamine 160205 223 (TreploW Products salt of a sulated Inc. alkyl phenoxypolyoxyethylene ether. 81... Warcolcnc W (War. Sulfated fatty acid 220225 Wick Chemical Co. ester. Dv. Suu Chemical Corp.).

Miscellaneous 82..- Alkagel (Amalga- Sodium oleyl 200 300 mated Chemicaltaurine. Corp.). 83..- Alrodync 315 (Alrose Polyethylene glycol 160 300Chemical Co.). fatty esters. 84..- Nil Diethanolamine.. 220 200 EstrononGel Conc. Sodium oleyl 210 205 Tigon Chemicals methyl tauride.

t 86.-- Igepon CN-42 (Gen- Sodium N -cyclo- 167 40 eral Dyestuii hexylN-palmi- Corp). toyl taurate. 87..- Maraspersc CE Calcium lignosul- 265300 (Marathon Corp.). fate. 88..- Mercin H (Sun Phosphorated oom- 285300 Chemical 0o.). plex alcohol. 89-.- Miranol SM Conc. Highly complex195 300 (Miranol Chemical amino sodium 0o.). fatty ac' 90.-- Moropon AC(More- Alkyl phenyl plus 265 300 tex Chemical oleyl taurate.

Products). 91..- Protenol KX (Con- Protein condensate.. 220 300 ineltalChemical o. 92--- SD-200 (13.1. du Pont Amine condensate-- 255 265 deNemours & Co.). 93..- Sellogen Conc. Methyltaurine 235 205 (lacques Wolf& condensate.

o. 94..- SotexN (Synthetic Long chain fatty `300 Chemicals Inc.). acidesters. 95... Sotex 384 (Synthetic .-...do 300 Chemicals Inc). 96..-laInol N (Rohm d: Sodium salt of a 156 190 Haas 00.). condensed sulionicacid. 97..- Wctsit W-1086 M Salt and solvent 255 155 (Jacques Wolf &free concentrated 0o.). alkyl aryl type.

lt is seen from the above table that la ylimited number ofagents-represented as Sipon LT-6,v Si-pon L-22, and Mirapon RK Conc. aresuitable :for use an ant-emulson agents in the system containing acopperuion` solvent 'of the type comprising an ammoniacal solution ofcopper ions with an anion capable of forming cuprous salts soluble insuch ammoniacal solution, for example, a copper ammonium acetate solventand C4 hydrocarbons, particularly a mixture of butadiene-1,3,n-butylenes, isobutylene and butanes. Such agents may be classifiedbroadly as anionic surface active agents derived from a fatty acidhaving 5-25 carbon atoms and a maximum of 3 oletinic linkages and of thegroup consisting of fatty alcohol amine sulfates, nitrogencontainingsalts of an alcohol sulfate and sulfonated fatty acid amide derivatives,particularly those in admixture with an aryl alkyl sulfonate.

Mirapon RK Conc. has been referred to heretofore by trade name only.Accordingly, the infra-red spectrum for Mirapon RK Conc. was obtained.The other two trade named products, Sipon LT6 and Sipon L22 are alreadycompletely identied. The spectrum is shown in the drawings in FIG. 1.'Ihe spectrum was obtained using a Beckman IR-3 spectrophotometer withthe sample prepared by mixing 0.005 gram of solid with 1.50 grams ofKBr. Characteristic absorption bands are exhibited at about thefollowing wave-lengths: an NH or OH absorption band at 3.0 microns,phenyl absorption at 3.2 microns, aliphatic CH at 3.4 and 6.8 microns, apossible amide carbonyl near 6.0 microns, an aromatic and/or C=C groupat about 6.2 microns, an aromatic group at about 6.3 microns, an NHgroup near 6.5 microns, an aromatic group such as a phenyl group at 6.6microns, a phenyl OH group or epoxide group or both at about 8.0 and 8.8microns, a possible SO3H group at 8.3-8.7 and 9.5-9.7 microns, and aparaphenyl and/ or epoxide and/or C=C group at about 11.0 and 12.3microns. The band at about 9.1 microns could be due to an electrolytesuch as sodium sulphate which is usually present in such compositions.

EXAMPLE I A series of tests was carried out, in which aqueous copperammonium acetate solvent containing varying amounts of dissolvedanti-emulsion being tested was mixed with and subsequently separatedfrom hydrocarbon mixtures containing varying concentrations ofbutadiene- 1,3, under the standard conditions of test I. The resultsobtained are summarized in Tables II, III and IV.

TABLE II Butadiene1,3 Concentration in Hydrocarbon Phase- 0.2 MolPercent Concentration oi compound, p.p.m 100 500 1,000

Compound Emulsion time (seconds) Sipon LT-tqriethanolamine salt otlauryl The emulsion time in the absence of any anti-emulsion agent was220 seconds.

TABLE III Butadene- 1,3 Concentration in Hydrocarbon Phase- 22.0 MolPercent Concentration of compound, p.p.m 100 500 1,000

Compound Emulsion time (seconds) Si on LT-6 104 83 65 Sigon L-22 117 6245 Mirapon RK Con 162 125 112 Emulsion time in the absence of anyanti-emulsion agent was 220 seconds.

8 TABLE 1v Batadt'ene-I,3 Concentration in Hydrocarbon Phase- 82.0 MolPercent Concentration of compounds, p.p.m. 200 500 600 Compound Emulsiontime (seconds) Sipon LT- 195 175 135 135 110 Sipon L-22 150 125 90 85 75Mirapon RK Conc 440 400 295 270 225 Emulsion time in the absence of anyanti-emulsion agent: for Mirapon RK Conc-490 seconds; for others- 220seconds.

It should be noted that there are two values of emulsion time shown forMirapon RK Conc. in Table IV. This is due to the fact that the emulsiontime for the solvent used with the Mirapon RK Conc. was 490 seconds inthe absence of anti-emulsion agent, while the solvent used with theother agents has an emulsion time of 220 seconds in the absence of anyanti-emulsion agent. Accordingly, the values obtained for Mirapon RKConc. in Table III were multipled by the factor in order to obtain avalue which could be compared with those obtained with a solvent havingan emulsion time of 220 seconds. The adjusted values are shown inparentheses.

The anti-emulsion agents tested in this example were Sipon LT-6 SiponL-22 and Mirapon RK Conc. since these were the only anti-emulsion agentsfound to be successful in this particular extraction process, as seenfrom the results in Table I.

It should be stressed that the use of compounds as anti emulsion agentswhich increase the emulsion time at any point of the extraction processis undesirable since such increase is indicative of increasedentrainment. Increased entrainment results in reduced operatingeiiciency because of the carry-over of hydrocarbon and/or solvent fromone settler to the next. To reduce entrainment and carry-over, more timemust be allowed to obtain a more complete separation of the hydrocarbonand aqueous phases in the settlers which, in turn, reduces thethroughput of the process. Accordingly, it is only through the use ofthe particular anti-emulsion lagents found to be useful in the presenceof low, intermediate and high concentrations of hydrocarbon that thebest and full advantages of the present invention are achieved.

EXAMPLE II Mirapon RK, which is `a surface active agent which was foundto be suitable for the breaking of emulsions in the specific systemherein studied, was then evaluated further, using concentrations in therange 0-3000 p.p.m. These tests were also performed using a mixture ofC4 hydrocarbons of varying composition. The results are shown in FIG. 2,which is a graph of the emulsion time, in seconds, versus the surfaceactive agent concentration in p.p.m. times 100.

EXAMPLE III entrainment is evidenced by an increase in the flow rate ofthe hydrocarbon phase from the settlers. The effect of Mirapon RK Conc.addition was tested by observing the hydrocarbon ow rate from the iirstsettler in the direction of hydrocarbon ow from the point of addition ofsolvent and the impure butadiene-1,3 stream to the system. When thisrate was high enough that it appeared an undesirable amount ofentrainment was occurring, ten gallons of an 18 percent solution ofMirapon in water were added. For a few minutes the entrainment becamemore severe, after which it decreased remarkably as shown in Table V.

Initial hydrocarbon iiow rate, lbs/hr.

Hydrocarbon flow rate after Mirapon addition, lbs/hr.

Run No.

However, it was found that the Mirapon RK Conc. was gradually lost fromthe system so that entrainment increased again very slowly. In practice,it has been found that at low feed rates entrainment is not a problembut, during periods of high production, it may be desirable to add suchanti-emulsion agent almost daily.

The data of Table V show the very marked reduction in entrainment whenMirapon is used to reduce emulsication.

What we claim is:

l. In the process of separating a conjugated diolen from a liquidmixture of such conjugated diolefin and other olefnic and saturatedhydrocarbons and which includes the steps of intimately mixing thehydrocarbon mixture with a solvent comprising an aqueous ammoniacalsolution of a copper salt comprising an anion capable of forming cuproussalts soluble in said ammoniacal solution; and allowing the mixture toseparate into a liquid hydrocarbon phase and a diolen-enriched liquidsolvent phase in a settler tank, the improvement which compriseseffecting such separation in the presence of an anionic Surface activeagent selected from the group consisting of the ammonium salt of laurylalcohol sulfate, the triethanolamine salt of lauryl alcohol sulfate anda mixture comprising a sulfonated fatty acid amide admixed with an alkylaryl sulfonate, said mixture exhibiting characteristic absorption bandsin the infra-red region of the spectrum when suspended in solidpotassium bromide at about the following wave-lengths expressed inmicrons: 3.0, 3.2, 3.4, 6.0, 6.2, 6.3, 6.5, 6.6, 6.8, 8.0, 8.3-8.7, 8.8,9.5-9.7, 11.0 and 12.3.

2. In the process of separating butadiene-1,3 from a liquid mixture ofbutadiene-1,3 and other oleflnic and saturated hydrocarbons and whichincludes the steps of intimately mixing the hydrocarbon mixture with anaqueous copper ammonium acetate solvent and allowing the mixture toseparate into a liquid hydrocarbon phase and a liquid butadiene-1,3enriched solvent phase in a settler tank, the improvement whichcomprises effecting such separation in the presence of a mixturecomprising a sulfonated fatty acid amide admixed with an alkyl arylsulfonate, said mixture exhibiting characteristic absorption bands inthe infra-red region of the spectrum when suspended in solid potassiumbromide at about the following wave lengths expressed in microns: 3.0,3.2, 3.4, 6.0, 6.2, 6.3, 6.5, 6.6, 6.8, 8.0, 8.3-8.7, 8.8, 9.5-9.7, 11.0and 12.3.

3. In the process of separating butadiene-1,3 from a liquid mixture ofbutadiene-1,3, n-butylene, isobutylene and butane and which includes thesteps of intimately mixing the hydrocarbon mixture with an aqueouscopper ammonium acetate solvent and allowing the mixture to separateinto a liquid butadiene-1,3 enriched aqueous solvent phase and a liquidhydrocarbon phase, the improvement which comprises effecting suchseparation in the presence of an anionic surface active agent which iseffective as an anti-emulsion agent in the presence of high and lowconcentrations of butadiene-1,3 in the presence of said aqueous copperammonium acetate solvent, said surface active agent being a mixturecomprising a sulfonated fatty acid amide admixed with an alkyl arylsulfonate, said mixture exhibiting characteristic absorption bands inthe infra-red region of the spectrum when suspended in solid potassiumbromide at about the following wave lengths expressed in microns: 3.0,3.2, 3.4, 6.0, 6.2, 6.3, 6.5, 6.6, 6.8, 8.0, 8.3-8.7, 8.8, 9.5-9.7, 11.0and 12.3.

4. The process of claim 3 wherein the surface active agent has aninfra-red absorption spectrum in which the absorptivity maxima occur atexactly the same wave lengths as those appearing in FIGURE l, whenmeasured on a sample prepared by mixing 0.005 part by weight of thesurface active agent with 1.50 parts by weight of potassium bromide.

5. In the process of separating butadiene-1,3 from a liquid mixture ofbutadiene-1,3 and other olenic and saturated hydrocarbons and whichincludes the steps of intimately mixing the hydrocarbon mixture with anaqueous copper ammonium acetate solvent and allowing the mixture toseparate into a liquid hydrocarbon phase and a liquid butadiene-1,3enriched solvent phase in a settler tank, the improvement whichcomprises effecting such separation in the presence of the ammonium saltof lauryl alcohol sulfate.

6. In the process of `separating butadiene-1,3 from a liquid mixture ofbutadiene-1,3 and other olenic and saturated hydrocarbons and whichincludes the steps of intimately mixing the hydrocarbon mixture with anaqueous copper ammonium acetate solvent and allowing the mixture toseparate into a liquid hydrocarbon phase and a liquid butadiene-1,3enriched solvent phase in a settler tank, the improvement whichcomprises eecting such separation in the presence of the triethanolaminesalt of lauryl alcohol sulfate.

7. In the process of separating butadiene-1,3, from a mixture ofbutadiene-1,3, n-butylene, isobutylene, and butanes and which includesthe steps of intimately mixing the hydrocarbon mixture with an aqueouscopper ammonium acetate solvent and allowing the mixture to separateinto a butadiene-1,3-enriched aqueous solvent phase and a hydrocarbonphase, the improvement which comprises eiecting such separation in thepresence of an anionic surface active agent which is effective as ananti-emulsion agent in the presence both of high and of lowconcentrations of butadiene-1,3 in the presence of said aqueous copperammonium acetate solvent, said surface active agent being the ammoniumsalt of lauryl alcohol sulfate.

8. In the process of separating butadiene-1,3, from a mixture ofbutadiene-1,3, n-butylene, isobutylene, and butanes and which includesthe steps of intimately mixing the hydrocarbon mixture with an aqueouscopper ammonium acetate solvent and allowing the mixture to separateinto a butadiene-1,3-enriched aqueous solvent phase and a hydrocarbonphase, the improvement which comprises effecting such separation in thepresence of an anionic surface active agent which is effective as anantiemulsion agent in the presence both of high and of lowconcentrations of butadiene-1,3 in the presence of said aqueous copperammonium acetate solvent, said surface active agent being thetriethanolamine salt of lauryl alcohol sulfate. y

References Cited in the file of this patent UNITED STATES PATENTS

1. IN THE PROCESS OF SEPARATING A CONJUGATED DIOLEFIN FROM A LIQUIDMIXTURE OF SUCH CONJUGATED DIOLEFIN AND OTHER OLEFINIC AND SATURATEDHYDROGARBONS AND WHICH IN CLUDES THE STEPS OF INITMATELY MIXING THEHYDROCARBON MIXTURE WITH A SOLVENT COMPRISING AN AQUEOUS AMMONIACALSOLUTION OF A COPPER SALT COMPRISING AN ANION CAPABLE OF FORMING CUPROUSSALTS SOLUBLE IN SAID AMMONIACAL SOLUTION AND ALLOWING THE MIXTURE TOSEPARATE INTO A LIQUID HYDROCARBON PHASE AND A DIOLEFIN-ENRICHED LIQUIDSOLVENT PHASE IN A SETTLER TANK, THE IMPROVEMENT WHICH COMPRISESEFFECTING SUCH SEPARATION IN THE PRESENCE OF AN ANIONIC SURFACE